Mercaptoazo and mercaptoazoxy aromatic compounds and method for the preparation thereof



monoalkylamino or dialkylamino, and hydrogen.

MERCAPTDAZO AND MERCAPTOAZOXY ARO- MATIC COMPOUNDS AND METHOD FOR THE PREPARATION THEREOF William E. Hanford and John W. Copenhaver, Short Hills, and Horace R. Davis, Cedar Grove, N.J., assignors to The M. W. Kellogg Company, Jersey City, N.J., a corporation of Delaware No Drawing. Filed Nov. 12, 1954, Ser. No. 468,554

11 Claims. (Cl. 260-143) in which R may be aryl, i.e., phenyl, diphenyl, or naphthyl, haloaryl, alkaryl in which the total number of carbon atoms in the alkyl portion does not exceed 10, i.e., the alkyl portion may be a single alkyl radical or a plurality thereof in which the total number of carbon atoms does not exceed 10, alkyl having from 4 to 20 carbon atoms, branched chain alkyl having from 4 to 7 carbon atoms, and benzyl radicals; and Y may be halo gen, alkoxy having not in excess of 20 carbon atoms,

alkyl having not in excess of 20 carbon atoms, amino, alkylarnino having not in excess of 20 carbon atoms in the alkyl portion, i.e., the alkylamino substituent may be Also, when Y is other than hydrogen, R may be a methyl, ethyl, or propyl radical.

States Patent Patented Sept. 4, 1962 0 T I N=N SR Vor O T N=N SR in which R may be aryl, i.e., phenyl, diphenyl, or naphthyl, haloaryl, alkaryl in which the total number of carbon atoms in the alkyl portion does not exceed 10, and the alkyl portion may be 1 or more alkyl radicals in which the total number of carbon atoms does not exceed 10, alkyl having from 1 to 20 carbon atoms, branched chain alkyl having from 4 to 7 carbon atoms, and benzyl VIII in which R may be aryl, i.e., phenyl, diphenyl, or naphthyl, haloaryl, alkaryl in which the total number of carbon atoms in the alkyl portion does not exceed 10, i.e., the alkyl portion may be a single alkyl radical or a plurality thereof in which the total number of carbon atoms does not exceed 10, alkyl having from 4 to 20 carbon atoms, branched chain alkyl having from 4 to 7 carbon atoms, and benzyl radicals; and Y may be halogen, alkoxy having not in excess of 20 carbon atoms, alkyl having not in excess of 20 carbon atoms, amino, alkylamino having not in excess of 20 carbon atoms in the alkyl portion, i.e., the alkylamino substituent may be monoalkylamino or dialkylamino, and hydrogen. Also, when Y is other than hydrogen, R may be a methyl, ethyl, or propyl radical.

in which R may be aryl, i.e., phenyl, diphenyl, or naphthyl, haloaryl, alkaryl in which the total number of carbon atoms in the alkyl portion does not exceed 10, and the alkyl portion may be 1 or more alkyl radicals in which the total number of carbon atoms does not exceed 10, alkyl having from 1 to 20 carbon atoms, branched chain alkyl having from 4 to 7 carbon atoms, and benzyl radicals.

Other compounds which may also be prepared according to the present invention are represented by the structural formulae:

in which R may be aryl, i.e., phenyl, diphenyl, or naphthyl, haloaryl, alkaryl in which the total number of carbon atoms in the alkyl portion does not exceed 10, and the alkyl portion may be 1 or a plurality of alkyl groups in which the total number of carbon atoms does not exceed 10, alkyl having from 4 to 20 carbon atoms, branched chain alkyl having from 4 to 7 carbon atoms, and benzyl radicals.

The reduction of aromatic nitro and nitroso compounds has been extensively studied and it is well known that from this reaction, according to the conditions, a variety of products may be obtained. Generally, the controlling factors are the type of reducing agent used and the acidity of the reaction mixture. In alkaline solutions and with a mild reducing agent, such as dry iron filings, the nitro compound is reduced to the nitroso compound, which through condensation is further reduced to the corresponding azo and azoxy compounds.

In accordance with the present invention, a one step synthesis consisting of the reaction of a mercaptan and a nitro or nitroso aromatic compound is carried out, preferably in an aqueous alkaline solution, at temperatures between 25 C. and 250 C., to prepare paraalkylmercapto and para-arylrnercapto mono and disubstituted azo and azoxyaromatic compounds.

It has been found that when a mercaptan is used as the reducing agent, in alkaline solution, the nitro aromatic compound, which may be substituted in the meta position, if desired, is not only reduced to the azo and/or azoxy form, but a para substitution of the aromatic ring by the alkylmercapto or arylmercapto group also takes place, thus providing a convenient method of synthesizing the afore described compounds.

The preparation described in the present invention is carried out in one step and with reactants which are readily available and relatively cheap. Furthermore, yields as high as 85.6 percent, based upon the nitrobenzene charged, have been obtained from the reaction of nitrobenzene with thiophenol and straight chain aliphatic mercaptans with one to four carbon atoms.

The starting materials involved in our method of synthesis embrace all the compounds in the mercaptan group and the nitro and nitroso aromatic compounds, which comprise (l) aromatic nitro and nitroso compounds consisting of the nitro or nitroso group substituted onto the aromatic ring such as in. nitrobenzene and nitrosobenzene; (2) aromatic nitro and nitroso compounds consisting of a nitro or nitroso group substituted onto the azoxy formations.

aromatic ring which has been further substituted with another aromatic ring or rings in such a manner as to form polycyclic aromatic compounds in which the position meta to the nitro or nitroso group is involved in the substitution, but in which the para-position is not, as in alpha-nitronaphthalene or alphanitrosonaphthalene; (3) aromatic nitro or nitroso compounds consisting of a nitro or nitroso group substituted on an aromatic ring which has been further substituted in the position meta to the nitro or nitroso group, as in m-nitrotoluene, m-nitroaniline, rn-nitro-N,N-dimethylaniline, m-nitroanisole, mchloronitrobenzene or m-bromonitrobenzene. For the purpose of this invention the term nitro and nitroso aromatic compounds will designate compounds conforming to the aforegoing description.

The compounds contained in this invention, due to their azo and azoxy configurations, are useful as insecticides, dyestuffs, dye intermediates and also as chemical intermediates. Their appearance is usually that of a crystalline solid ranging in color from yellow to orangered. Conforming to the general properties attributed to other classes of substituted azo and azoxy compounds, they are as a rule insoluble in water, unattacked by alkali and dilute acids, stable to heat, and crystallize well. They produce a dark violet color with concentrated acids, an effect characteristic of substituted azo and azoxy sulfides and not reproducible with azo and azoxybenzene.

The ratio of mercaptan to the nitro or nitroso aromatic compound is above 2:1 and preferably between 2:1 and 8:1 depending upon the individual mercaptan used. Increased molar ratios of aliphatic mercaptans to nitro or nitroso compounds decrease the amount of yield, while increased molar ratios of aromatic mercaptans slightly increase the yield. The optimum concentration of the mercaptan is usually about four moles per mole of the nitro or nitroso aromatic compound, although the final product results from an equimolar combination of the reagents. The mercaptan serves a two fold purpose in that it not only substitutes into the aromatic ring, but also reduces the nitro and nitroso groups to the azo and The relative amounts of azo and azoxy compounds produced are dependent upon the mercaptan used and the conditions under which the reaction is carried out.

Some type of basic material is essential to this syn- 1 thesis, the hydroxides of the alkali metals being preferable. Nevertheless, organic, basic materials such as alkali metal alcoholates or amines may also be used, al though they are not as effective as the inorganic bases for promoting the substitution of the mercaptan groups into the aromatic nucleus.

The quantity of base used may range from molar concentration slightly in excess of the mercaptan molar concentration to a saturated solution of the base in the solvent employed. A molar ratio of alkali to mercaptan greater than 4:1 is preferable in these reactions.

Water is the most satisfactory medium in which to carry out the reaction; however, alcohols, liquid amines, or inert solvents may be used if desired.

The reaction may be operated at temperatures between 25 C. and 250 C. or below the decomposition temperature of the desired product. Although reaction does take place at temperatures below 25 C., the rate of reaction is not sufficiently great to produce any yield of the product within a reasonable period of time. At temperatures above about 250 C., excessive decomposition of the desired product occurs. For convenience in operation and to obtain the most desirable reaction rates, temperatures ranging from 60 C. to 175 C. are preferable for the synthesis of the desired products from nitro compounds. Similar reactions carried out with nitroso compounds as the starting material should be operated at temperatures between 25 C. and C.

More specifically, the procedure is as follows: the nitro or nitroso aromatic compound, the mercaptan, and the aqueous alkali are placed in a vessel. The vessel may be glass if the temperature is not to exceed 105 C. If the reaction is to take place at about room temperature, no additional equipment is required. At temperatures above room temperature, a reflux condenser should be used. At temperatures higher than 105 C., the water tends to boil out of the reaction zone, and it, therefore, becomes necessary to use some type of pressure equipment, designed more to retain the water vapor in the system than to exert pressure on the area of reaction. Equipment such as a sealed bomb, an autoclave, or water tight apparatus for continuous operation may be employed. Throughout the temperature range agitation has been found to be advantageous but not essential for the reaction to proceed. The preferred method is to heat the mixture containing an aromatic nitro starting material to a temperature between 60 and 175 C. At temperatures between 80 C. and 105 C. the reaction will go to completion in 20 to 48 hours, while at a temperature of 140 C. the required reaction time is 5 to hours. Syntheses from aromatic nitroso starting materials require l to 4 hours at temperatures of 25 C. to 50 C.

Upon completion of the reaction, the unreaoted aromatic nitro or nitroso compound and/or the extraneous disulfide of the mercaptan is removed by steam distillation or any other convenient method. The para-alkylmercapto or para-arylmercapto substituted azo and azoxy compounds are extracted with a suitable solvent or any other applicable method. The products are then recovered by recrystallization or chromatography.

Individual compounds, prepared by our method of synthesis, and the starting materials used are compiled in Table I. The operating data from some of the syntheses carried out are compiled in Table II, to illustrate more fully the variation of conditions employable for the reaction.

The invention will be further illustrated by reference to the following specific examples:

EXAMPLE I Reaction of Benzylmercaptan with Nitrobenzene A mixture consisting of 0.3 mole of nitrobenzene, 1.2 moles of benzyl mercaptan, 480 ml. of water and 3 moles of solid sodium hydroxide was placed in a glass flask. A reflux condenser and a mechanical stirrer were connected. The mixture was then heated to a temperature of 102 C. and the reaction of the components proceeded COMPOSITION p,p-B is (benzylmercapto) azobenp-B enzylmercaptoazobenzene zene Percentages Percentages Elements Elements Found Calculated Found Calculated Carbon 73. 10 73. Carbon. 74. 79 74. 96 Hydrogem. 5. 20 5. 20 Hydrogen. 5. 40 5. 30 Sulfur 15. 03 14. 70 N itrogen 9. 42 9. 21 Sulfur... 10. 32 10. 53

The p,p-bis(benzylmercapto)azobenzene was reduced with stannous chloride and treated with acetic anhydride to form the previously reported derivative P'benzylmercaptoacetanilide (M.P. 117.5 -1 19 C.)

EXAMPLE II Reaction of Nitrobenzene and n-Butyl Mercarptan A mixture of 0.2 mole of n-butyl mercaptan, 0.05 mole of nitrobenzene, 230 ml. of methanol and 0.5 mole of solid sodium methylate was placed in a glass flask. A reflux condenser and a mechanical stirrer were attached. The mixture was then heated to a temperature of 65 C. and refluxed for seventeen hours. At the end of this time the mixture was steam distilled in a conventional manner to remove excess methanol, nitrobenzene, and the corresponding disulfide of the mercaptan. The products, consisting of p,p-bis(n-butylmercapto) azoxybenzene, p,p'-(n-butylmercapto)azobenzene, p-n-butylmercaptoazoxybenzene, and p-n-butylmercaptoazobenzene, were removed from the residue of the steam distillation by extraction with chloroform and thereafter recovered and separated by chromatography.

The main products were of the disubstituted types, represented by p,pbis(n-butylmercapto)azoxybenzene and p,p'-bis(n-butylmercapto)azobenzene. The results found in the analysis for the elements of these compounds agreed well with the calculated theoretical values.

COMPOSITION p,p-Bis(butylmercapto) p,p-l3is(butylmercapto) azobenazoxybenzene zene Percentages Percentages Elements Elements Found Calculated Found Calculated Carbon Hydrogem. Nitrogen" Sulfur EXAMPLE III Reaction of Nitrosobenzene and Thiophenol Thiophenol (16.5 g., 0.15 mole) was dissolved in 500 grams of 10 percent sodium hydroxide solution and the mixture was stirred at room temperature while nitrosobenzene (10.0 g., 0.093 mole) was added in small quantities over a period of twenty minutes, during which brown fumes were evolved. The mixture was tirred but not heated for an additional three hours. At the end of this time it was steam distilled in a conventional manner to remove excess nitrosobenzene. The products were then extracted from the residue of the steam distillation with benzene and separated chromatographically on alumina. By identification through melting points and mixed melting points, the products were found to be P p'-bis (phenylmercapto)azoxybenzene (5.0 percent yield), p-phenylmercaptoazoxybenzene (2,3 percent yield) and azoxybenzene (39 percent yield).

7 EXAMPLE 1v Reaction of Nitrobenzene and Thiophenol in Triethyl Amine A mixture consisting of 0.05 mole nitrobenzene, 0.2 mole thiophenol and 1.14 moles triethyl amine was placed in a glass flask. A reflux condenser and a mechanical stirrer were attached. The mixture was then heated to a temperature of 89-90 C., which is the boiling temperature of triethyl amine, and refluxed for thirty-six hours; At the end of this time, the triethyl amine was removed by heating the mixture on a steam bath. The residue was then steam distilled in a conventional manner to remove unreacted nitrobenzene. The products were removed from the residue of the steam distillation by extraction with chloroform. The products were isolated chromatographically on alumina. There was no evidence that substituted azo or disubstituted azoxy compounds were formed. p-Phenylmercaptoazoxybenzene was produced in a 2.6 percent yield. The results of the analysis of the percentage composition of this compound agree well with the calculated values.

Reaction of Thiophenol With m-Snbstitnted Nitroaromatic Compounds A group of m-substi-tuted nitroaromatic compounds consisting of m-nitrotoluene, m-nitroaniline, mnitro-N,N1 dimethylaniline, m-nitroanisole, m-chloronitrooenzene, and m-bromonitrobenzene were used as individual starting materials along with thiophenol in the same procedure as used with nitrobenzene and mercaptans described in Example I. Thiophenol (0.40 mole) was dissolved in 600 g. of 20 percent aqueous sodium hydroxide, to this was added the nitro-aromatic compound (0.10 mole). The mixture was refluxed for 20 to 48 hours. In these cases steam distillation was omitted. The products were extracted directly from the mixture with benzene and recovered chromatographically on alumina. The compounds recovered in such a manner conformed to the general formula:

Y O Q RS N= SR COMPOSITION [p,p-Bis(phenylrnereapto)-m,m-bis(amino)azoxybenzene] Percentages Elements Found Calculated Carb 64. 49 64. 84 Hydro en 4. 48 4. 54 Nitr n 12. 94 12. 60 Sulfur 14. 09 14. 42

[p,p-Bis(phenylmercapto)-m,m-bis(methyl)azoxybenzene] Percentages Elements Found Calculated Carbon 70. 55 70. 65 Hydro en 5. 0l 4. 81 N itrmzen 6. 33 5. 77 Sulfur 14. 49 14. 41

[p,p-Bis(phenyl1nereapto)-m,m-bis(ehloro)az0xybenzene] Percentages Elements Found Calculated Carb 59. 62 59. 93 Hydro en 3. 34 3. Nitrogen 5. 80 6.04 14. 67 14. 92

[p,p-Bis(phenylmercapto)-m,m'-bis(bromo)azoxybenzene] Percentages Elements Found Calculated Carb 50. 36 49. 70 Hydrogen 2. 82 2. 98 Sulfur 11. 20 10. 74

EXAMPLE VI Reaction of Alpha-Nitronaphthalene and T hiophenol The procedure was the same as used with nitrobenzene and mercaptans. A mixture consisting of 0.40 mole of thiophenol, 0.10 mole of alpha-nitronaphthalene and 600 g. of 20 percent aqueous sodium hydroxide solution was stirred and refluxed at a temperature of C. for 21 hours. In this case steam distillation was omitted. The desired products were extracted directly from the mixture with benzene and were then isolated chromatographically on alumina. The main product conforms to the structure configuration,

which is another meta-substituted form of the general Formula II. Analysis of the product yielded the following results:

9 dium hydroxide was placed in a bomb. The mixture was then heated to 140 C. and agitated for eight hours. At the end of this time, the mixture was steam distilled to remove the unreacted nitrobenzene. From the residue of the steam distillation, the products were extracted with chloroform and recovered through recrystallization. The products were predominately of the azoxy type. p,p'-Bisl9 (phenylmercapto)azoxybenzene was obtained in a 12.1 percent yield and p-phenylrnercaptoazoxybenzene in a 20.3 percent yield.

When this reaction was operated for 42 hours at a temperature of 108 C., the percent yield was 27.7 percent of p,p'-bis(pheny1mercapto)azoxybenzene and 24.3 percent of p-phenylmercaptoazoxybenzene.

Table I COMPOUNDS WHICH HAVE BEEN ISOLATED Starting material Product Mercaptan Nitro or nitroso Structural formula Empirical formula M.P.,O.

% 1 ThiophenoL. l/nitrosoben- QSC N=NOSC CMIHISNzSzO 121 -122 zene, 2/nitr0- benzene.

g 2 n-Buiylmer- Nitrobenzene CH3(CH)3S N=N C S(CH2)aCH3 CZOHQBNZSZO 79 79.5

cap 811.

g 3 t-Butylmer- .dQ (CH3)3OSC -N=NQSO(CH3)3 CzoHggNzSgO 120 captan.

HsC g CH3 4 ThiophenoL- m-Nitro- Qs-QrmrzOsG C26H22N2S20 104 -105 toluene.

01 19 Cl 5 S -N:N@ S@ benzene.

Br g Br 6 do m-Br0monitro- -s N=NS Cz4I'I sN2BI2SZO us -120 benzene.

H2N (1? NH2 7 d0 m-Nitroaniline --SC N=N S CitHtONiSBO 145 -14s.5

g 8 Benzyl mer- Nitrobenzene C N=NOSCEDO 1' CwHmNzOS 64 65 captan.

C1 C1 9 Thiophenol m-Nitrochloro- SN=NC SC C24Hit 2 12 2----- 174 175 benzene.

10 t-Butyl mer- Nitrobenzene (OH3)3CSN=N SO(CHa)z CzoHzuNzSz 171 captan.

11 n-ButylmerdO CH3(OH2)3S N=N S(CI*I2)3CH3 CznHzeNzSz 98 99 captan.

12 Benzylmerdo Octane N=NOSCHZ CgoHzzNgSz 182 -1s4 captau.

13 -...do 1o c N=N-scm OIQHMNZS 1015-108 i 14 Thiophenol" Nit onaphtha Os N=1-r -s Ca2H22N2S2O 198 -200 ene.

g 15 p-ThiocresoL..Nitrobenzene HBCOSON=NOSQOHS CwHzz zOSz 136 OII3O T 0 00113 16 ThiophenoL. m-Nitroanisole- -S 3N=NC S 3 CzeH22NzO3Sz 116 -118 (CHmN O N(CH3)2 l T l 17 d0 m-Nitr0-N,N- -S N=N S O2BH2BN2OS2 138 --140 dimethylaniline.

TIhe configuration as shown is not to be construed so as to limit the position of the oxygen in the diazoxy group It may be bonded to either nitrogen atom.

Table II OPERATION DATA OF ILLUSTRATIVE REACTIONS Primary Secondary Reactants Reaction media Conditions product product Nitro or nitroso aromatic com- Vol. Time Temp. Per- Per- Mercaptan Moles pound Moles Solvent in ml. Alkali Moles h in C. Type cont Type cont ours Methyl mercaptan. 0. 20 Nitrobenzene 0.05 H20 80 NaOH 0.5 140 II 23. 6 XII 10.1 Do 0.5 H20 800 NaOH 5. 00 1 48 109 XII 4. 4 II 4.0 Ethyl mercaptan... 0. I110 160 NaOH 1.00 48 40 II 11. 3 XII 7.1 Do 0. 05 H20 80 NaOH 0. 50 8 140 XII 26. 3 II 25.9 Do 0.50 E20 800 NaOH 5. 00 41 80 XII 48. 1 II 37. 5 n-Propyl mercaptan 0. I120 360 NaOH 2. 25 24 82-110 XII 43. 1 II 20. 5. n-Butyl mercaptan O. 05 1120 80 NaOH 0. 50 9 140 XII 11. 8 XI 10. 3

D 0. 10 E 480 NaOH 3. 00 20 105 XII 14. 4 0. E20 240 NaOH 1. 50 24 105 XII 3. 9 0.05 MeOH 325 LiOMe 0. 50 22 65 XII 13. 4 0. 50 MeOH 230 NaOMe 0. 50 17 65 XII 16. 4 XI 14.8 0. 10 E20 70 NaOH 0.50 9 140 XI 28. l XII 20. 2 0.05 E20 80 NaOH 0. 50 8 140 II 20. 3 XII 12. l 10 0. 05 I120 80 NaOH 0. 50 7 140 II 10. 1 XII 6.0 0. 50 H20 800 NaOH 5. 00 48 108' XII 27. 7 II 24. 3 0. 06 I120 240 NaOH 1.50 28 105 XII 5. 7 0.05 E10 480 NaOH 3.00 48 105 XII 19.5 II 8. 4 0. O5 H20 480 NaOH 3. 00 48 105 XII 24. 5 II 18. 8 0.05 E20 480 NaOH 3. 00 48 105 XII 35. 2 II 2. 0 0. 05 1120 570 NaOH 0.75 48 100 XII 1. 5 II 1. 4 0. 05 H20 480 NaOH 8. 00 24 110 XII 28. 6 II 15. 7 0. 05 EI3N 160 ETQN 1. 14 36 89 II 2. 6 0.30 E20 480 NaOH 3. 00 12 102 XI 6. 7 I 6. 5 0.05 1120 80 NaOI-I 0. 50 8 140 I 12. 1 XI 1.2 0. 10 I120 480 NaOH 3. 00 105 VIII 26. 6 0. 40 rn-Nitrotoluene 0- 10 E20 480 NaOH 3. 00 36 105 III 16. 0 0.40 m-Nitloaniline 0. 10 E20 480 NaOH 3. 00 24 105 VIII 30.0 O. 40 m-Nitroehlorobenzene... 0. 10 E20 480 NaOH 3.00 29 105 VIII 34.0 VII 1. 5 0. 40 m-Nitrobromobenzene 0. 10 E20 480 NaOH 3. 00 2 105 VIII 40. 0 0. 40 N,N-dimethyl-m-nitroaniline 0. 10 E20 480 NaOH 3. 00 43 105 VIII 4. 0 0. 40 m-Nitroanisol 0. 10 H20 400 NaOH 2. 00 20 105 VIII 23. 5

1 No agitation. 2 None isolated.

EXAMPLE VIII ThlS application 1s a contmuatron-m-part of copendmg To demonstrate the efficacy of the compounds of the invention as insecticides, test solutions of various compounds of the invention were injected into the blood stream of the American roach (Periplaneta americana). Mortality readings were made every 24 hours for a period of six days, at which time total mortality was recorded. The standard concentration of material commonly used in this test is 2.5 percent, but as the compounds of the invention were insoluble to this extent, a saturated supernatant liquid was used. The solvent consisted of 10 percent by weight acetone, 10 percent by weight xylene, 5 percent by weight ethanol, and 75 percent by weight Deo Base. (Footnote at bottom of column 12.)

The results are as follows:

AMERICAN ROAOH INJECTION [Dosagez 0.008 and 0.012 ml. for male and female roach respectively o saturated solutions. Six clay count] Material Sex Percent Mortality 4,4-bis(phenylmercapto)azoxybenzene 5i 8% 4,4-bis(pheny1mercapt0)azobenzene FM 4- benz lmerca to azobenzene F 0 y p M 100 4,4-bis(benzylmercapto)azobenzene lF/l 4,4-bis(ethylsulionyl)azobenzene 1% 48 4,4 bis(phenylmereapto) -3,3 bis (amino) azoxyben- F 0 zene.

M 60 5 4,4 bis (phenylmercapto) -3,3 -bis (chloro) azoxyben- F 20 zone.

M 40 4,4'-bis(phenylmercapto)-3,3-bis(ch1oro)azobenzene. lF/I 4,4 bis(phenylmercapto) 3,3 bis(methoxy) azoxy- F 20 benzene.

M 60 4,4-bis(ethylmercapto)-3,3-bis(ch1oro)azoxybenzene {a 4g NOTE.-DDT male roach 0.075 ml., percent mortality; DDT female roach 0.04 ml. percent mortality. Control, male 20 percent mortality; fem ale 0 percent mortality.

application Serial No. 282,716 filed April 16, 1952, now abandoned.

It will be obvious to those skilled in the art that many modifications may be made within the scope of the present invention without departing from the spirit thereof, and the invention includes all such modifications.

We claim:

1. Compounds having the formula:

in which X is selected from the group consisting of azo and azoxy groups; R is selected from the group consisting of phenyl, diphenyl, naphthyl, halophenyl, and alkylphenyl radicals in which the total number of carbon atoms in the alkyl portion does not exceed 10, an alkyl radical having from 1 to 20 carbon atoms, and a benzyl radical; and Y is a dialkylamino radical in which each alkyl radical has not in excess of 10 carbon atoms.

2. Compounds having the formula:

A light petroleum distillate which has been refined to complete freedom from kerosene odor and which is used as a solvent for waxes, oils and petrolatums and is miscible with organic solvents. Deo Base as a product of L. Sonneborn Sons, Inc. has an API specific gravity of 48/51 and other properties reported in L. Sonneborn Sons Technical Data File DB entitled Deo Base.

13 5. A process which comprises reacting a mercaptan having the formula RSH wherein R is selected from the group consisting of phenyl, diphenyl, benzyl, naphthyl, and halophenyl radicals, an alkyl phenyl radical in which the total number of carbons in the alkyl portion does not exceed 10, an alkyl radical having not in excess of 20 carbon atoms, a branched chain alkyl radical having from 4 to 7 carbon atoms, with a substituted benzene compound having the formula wherein Z is selected from the group consisting of nitro and nitroso radicals and Y is selected from the group consisting of hydrogen and halogen atoms, an amino radical, an alkoxy, alkyl and alkylamino radicals having not in excess of 20 carbon atoms in the alkyl portion; in an alkaline medium at a temperature of between about 25 C. and about 250 0., the mol ratio of mercaptan to substituted benzene being in the range of from about :1 to about 8: 1, to produce the corresponding compounds selected from the group consisting of a mercaptoazo benzene and a mercaptoazoxy benzene.

6. A process for preparing compounds selected from the group consisting of mercaptoazobenzenes and mercaptoazoxybenzenes, which comprises reacting a mercaptan having the formula RSH in which R is selected from the group consisting of naphthyl, diphenyl, phenyl, halophenyl, and alkylphenyl radicals in which the total number of carbon atoms in the alkyl portion does not exceed 10, an alkyl radical having from 4 to 20 carbon atoms, a branched chain alkyl radical having from 4 to 7 carbon atoms and a benzyl radical, in an aqueous alkaline medium at a temperature of between about 25 C. and about 175 C. and a substituted benzene having the formula in which Z is selected from the group consisting of nitro and nitroso radicals and Y is selected from the group consisting of halogen, alkoxy having not in excess of 20 carbon atoms, alkyl having not in excess of 20 carbon atoms, amino, alkylamino having not more than 20 carbon atoms in the alkyl portion and hydrogen; the molar ratio of mercaptan to substituted benzene being in the range of about 2:1 to 8:1.

7. A process for preparing compounds having the formula:

in which X is selected from the group consisting of azo and azoxy groups; R is selected from the group consisting of a phenyl, diphenyl, naphthyl, halophenyl, alkyl phenyl radical in which the total number of carbon atoms in the alkyl portion does not exceed 10, alkyl having from 4 to 20 carbon atoms, branched chain alkyl having from 4 to 7 carbon atoms, and benzyl radicals; and Y is selected from the group consisting of halogen, alkoxy having not in excess of 20 carbon atoms, alkyl having not in excess of 20 carbon atoms, amino, alkylamino having not in excess of 20 carbon atoms in the alkyl portion, and hydrogen, which comprises reacting in an alkaline medium at a temperature in the range of about 25 C. to about 250 C., a mercaptan having the formula RSH in which R is a given above and a substituted benzene having the formula in which Z is selected from the group consisting of nitro and nitroso radicals and Y is as given above, the molar ratio of mercaptan to substituted benzene being in the range of about 2:1 to about 8:1.

8. A process for preparing compounds selected from the group consisting of mercaptoazobenzenes and mercaptoazoxybenzenes which comprises reacting, in an aqueous alkaline medium at a temperature in the range of about 25 C. to about 250 C., a mercaptan having the formula RSH in which R is selected from the group consisting of phenyl, diphenyl, naphthyl, halophenyl and alkyl phenyl radicals in which the total number of carbon atoms in the alkyl portion does not exceed 10, an alkyl radical having not in excess of 20 carbon atoms, a branched chain alkyl radical having from 4 to 7 carbon atoms and a benzyl radical and a substituted benzene having the formula in which Z is selected from the group consisting of nitro and nitroso radicals and Y is selected from the group consisting of halogen, alkoxy having not in excess of 20 carbon atoms, alkyl having not in excess of 20 carbon atoms, amino, alkylamino having not in excess of 20 carbon atoms in the alkyl portion, and hydrogen; the molar ratio of mercaptan to substituted benzene being in the range of about 2:1 to 8:1.

9. A process according to claim 8 in which the alkaline medium is an aqueous solution of an alkali metal hydroxide.

10. A process according to claim 7 in which the alkaline medium is a trialkyl amine.

11. A process according to claim 7 in which the alkaline medium is an alcoholic solution of an alkali metal alcoholate.

References Cited in the file of this patent UNITED STATES PATENTS 2,064,332 Zwilgmeyer Dec. 15, 1936 2,200,006 McNally et a1 May 7, 1940 2,213,218 Hester Sept. 3, 1940 2,647,113 Lanty et al July 28, 1953 OTHER REFERENCES Bielstein, 4th ed., vol. 16 (1934), pp. 239, 240, 385, 386.

Frear et al.: Journal of Economic Entomology, vol. 40, (1947), p. 736-741.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, $052,667 September 4 1962 William E, Haniord et alo It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 6 line 20, for "p p =(n-butylmercapto)azobenzene" read p,p bis(nbutylmercapto)azobenzene line 74 for "23" read 2,,3 columns 9 and 10 Table I fourth column the ninth formula should appear as shown below instead of as in the patent:

same Table I fourth column the sixtecrth formula should appear as shown below instead of as in the patent:

OCH

CH O 0 same Table I, fourth column. the seventeenth formula should appear as shown below instead of as in the patent:

(CH3)2N N(CH3) column 14, line 9, for "a", first occurrence read We as Signed and sealed this 21st day of May 1963.

(SEAL) Attest:

ERNEST We SWIDEII DAVID L, LADD Attesting Officer Commissioner of Patents 

